CN107303486A - A kind of Hydrobon catalyst and preparation method thereof - Google Patents
A kind of Hydrobon catalyst and preparation method thereof Download PDFInfo
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- CN107303486A CN107303486A CN201610262161.7A CN201610262161A CN107303486A CN 107303486 A CN107303486 A CN 107303486A CN 201610262161 A CN201610262161 A CN 201610262161A CN 107303486 A CN107303486 A CN 107303486A
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- hydrobon catalyst
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- catalyst
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- terephthalaldehyde
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/41—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention relates to a kind of Hydrobon catalyst, it is made up of following component：Counted using the gross weight of Hydrobon catalyst as 100%, the content of manganese oxide is 5~20wt%, and the content of cerium oxide is 5~20wt%, and surplus is aluminum oxide.Manganese compound will be contained using the method for spray or dipping and cerium-containing compound solution is contacted with alumina support, through drying, high-temperature roasting, that is, the catalyst is made.The present invention catalyst can as dimethyl terephthalate (DMT) Hydrobon catalyst, conversion ratio and terephthalaldehyde (TPAL) selectivity with higher dimethyl terephthalate (DMT), make the technological process of production terephthalaldehyde easier, suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of the catalyst for hydrogenation reaction, more particularly to for dimethyl terephthalate (DMT)
Hydrobon catalyst preparation method.
Background technology
Terephthalaldehyde is a kind of micro- yellow to white, needle-shaped crystals powder, 112~117 DEG C of fusing point.Terephthalaldehyde is organic
Synthesis and the important intermediate of Polymer Synthesizing.It has two active aldehyde radicals, therefore, it can autohemagglutination, again can with it is other
Unit copolymerization forms the compound of various performances.Terephthalaldehyde is mainly used in fluorescent whitening agent and synthetic plastic, is synthesis
The primary raw material of double styrene fluorescent bleaches, is mainly used in the works such as plastics, spices, medicine, fuel, fluorescent whitening agent
Industry.Recently, one of application field of terephthalaldehyde is the special fibre for armored fabric, such as bullet-proof vest, fire-retardant clothing
Thing and space suit.
At present, traditional two-step method still follows in the production most domestic manufacturing enterprise of terephthalaldehyde, and synthetic route includes
The chlorination of paraxylene and the hydrolysis of xylene chloride, the method are harmful to environment, and in industrial-scale production be without
Ji.It is a kind of new of current terephthalaldehyde production to produce terephthalaldehyde using air oxidation process catalysis oxidation paraxylene
Type process route, its technological process is simple, environmentally friendly, there is fine development prospect.In paraxylene (PX) air
In oxidizing process, existing liquid phase component has solid phase components again, and its product is more complicated, and primary product has p-tolyl aldehyde
(TALD), p-methylbenzoic acid (PT), terephthalaldehyde (TPAL), terephthalic acid (TPA) (TA), p -carboxybenzaldehyde (4-CBA)
Deng.Many researchs have been done in this field by gas chemical company of Mitsubishi, Yi Siman, Princeton chemical research company etc..
Chinese patent CN103508862A (a kind of method that catalysis oxidation prepares terephthalaldehyde) is catalyzed using fluorination reagent
Sodium chloride obtains exclusive product to benzene dichloro, and benzene dichloro is reoxidized and obtains terephthalaldehyde, and oxidising agent used is titanium dioxide
Manganese, adding the enhancing of 98wt% sulfuric acid catalysis oxidation effectiveness makes to raise benzene dichloro conversion ratio, but technical process is relatively complicated, holds
It is also easy to produce more impurity.
Fe2O3There is activity well in the oxidation reaction, but selectivity is very poor, using Fe to MoO3It is modified to prepare Fe-Mo
Catalyst is widely used in the reaction of prepn. of formaldehyde by oxidation of methanol and toluene oxidation producing benzaldehyde, and obtains preferable effect.
But for influenceing the factor also ununified final conclusion of Fe-Mo catalyst catalytic performances, carrying out prepn. of formaldehyde by oxidation of methanol
In research, Fe-Mo catalyst catalytic performances depend on n (Fe)：n(Mo).Fe2(MoO4)3It is Fe-Mo catalyst
Effective active component, but in prepn. of formaldehyde by oxidation of methanol reaction, find the best catalyst n (Fe) of activity：N (Mo) is less than
Fe2(MoO4)3The catalyst stoichiometrically prepared.
Guangzhou University Liu rely on oneself seminar using incorporation Ni method Fe-Mo catalyst is modified, be catalyzed Fe-Mo
The performance and activity stability of agent are improved.Ni incorporation improves Fe-Mo catalyst to paraxylene Selective Oxidation
The catalytic performance of terephthalaldehyde.It it is 450 DEG C in reaction temperature, air and paraxylene velocity ratio are 150000, air speed
For 25h-1Under, the conversion ratio of paraxylene is 80.3%, and the selectivity and yield of terephthalaldehyde are respectively 47.7% He
38.3%, and the active lifetime of catalyst is improved.But this catalyst preparation process is complicated and expensive, no
Too suitable industrially scalable.
Recently, LG chemical companies release the new technology that direct oxidation method produces terephthalaldehyde.With conventional two-step process
Compare, new technology need not use chlorine, more environmentally friendly.New technology is using special mixed-metal oxides as urging
Agent, carries out selective oxidation reaction under 500~600 DEG C, normal pressure, reacts in canned multitube fixed bed
Carried out in reactor.Experiment display, the conversion ratio of paraxylene to terephthalaldehyde is 70~78%, and selectivity is 70~80%,
Test conversion ratio and selectivity is not still high.
In terms of terephthalic acid (TPA) (or vinegar) reduces the research of terephthalaldehyde processed, South Korea Gyongsan, Yeungnam is big
Learn department of chemistry and obtain greater advance, with terephthalic acid (TPA) (ester) for raw material, prepared by catalyst of 9-BBN using method of hydrotreating
The report of terephthalaldehyde, the yield of terephthalaldehyde can reach 92%.But terephthalic acid (TPA) (ester) is reduced into benzene two
Formaldehyde is still undesirable.
The content of the invention
Purpose of the present invention catalyst used when being for producing terephthalaldehyde using paraxylene in the prior art is brought
The problem of make the technological process of production terephthalaldehyde easier there is provided a kind of Hydrobon catalyst, the catalyst, and
And the selectivity and yield of terephthalaldehyde are higher.
Another object of the present invention also resides in the preparation method for providing above-mentioned Hydrobon catalyst.
Technical scheme
A kind of Hydrobon catalyst, is made up of following component：Counted using the gross weight of Hydrobon catalyst as 100%, manganese oxide
Content be 5~20wt%, the content of cerium oxide is 5~20wt%, and surplus is aluminum oxide.
The preparation method of above-mentioned catalyst：Solution containing manganese compound and cerium-containing compound solution are first prepared respectively, must be mixed after mixing
Solution is closed, mixed solution is contacted with alumina support, through drying, high-temperature roasting, finally leads to hydrogen reducing, produces this hair
Bright Hydrobon catalyst, it is support type MnO2-CeO2/Al2O3Catalyst.
In above-mentioned preparation method, described solution containing manganese compound is any of manganese chloride, manganese acetate, manganese nitrate solution
Or two or more combinations, cerium-containing compound solution be any of cerium chloride, cerous nitrate, cerous acetate solution or two kinds with
On combination.
In above-mentioned preparation method, the method that the mixed solution is contacted with alumina support is spray or impregnates, and time of contact is
0.1~10h.
In above-mentioned preparation method, alumina support 100~200N/cm of compression strength, 150~300m of specific surface area2/g.Oxygen
Change the customary preparation methods of alumina supporter：By boehmite powder with containing water, binding agent methylcellulose, peptizing agent nitric acid
Gel mediated on kneader uniformly, material extrusion molding on banded extruder after kneading, and through drying, roasting after obtain.
In above-mentioned preparation method, the temperature of the drying is 80-120 DEG C, and the time is 2-10h.
In above-mentioned preparation method, the temperature of the high-temperature roasting is 300-600 DEG C, and the time is 1-10h.
In above-mentioned preparation method, the temperature of the logical hydrogen reducing is 300-350 DEG C, and the time is 2-6h, hydrogen flowing quantity 3L/h.
Using above-mentioned Hydrobon catalyst produce terephthalaldehyde method (described activity rating be microreactor dress
Put middle progress)：The above-mentioned Hydrobon catalysts of 30ml are loaded into reactor, are first prepared by solvent of Isosorbide-5-Nitrae dioxane
5% dimethyl terephthalate (DMT) solution be raw material, feed rate be 0.6~2ml/min, 350~380 DEG C of reaction temperature, instead
8h between seasonable, produces terephthalaldehyde.
Beneficial effect：The Hydrobon catalyst of the present invention has the conversion ratio of higher dimethyl terephthalate (DMT) and to benzene two
Formaldehyde (TPAL) selectivity, makes the technological process of production terephthalaldehyde easier, suitable for industrialized production.
Embodiment
The embodiment to the present invention is described in detail below, it should be noted however that the protection of the present invention
Scope is not limited to these specific embodiments, but determined by claims.
Remarks：In following embodiments, when producing terephthalaldehyde using the Hydrobon catalyst of the present invention, final sample contains
Using Shimadzu LC-10 high performance liquid chromatographs, (C18 posts, mobile phase is the CH of mass fraction 10% to amount3CN and 0.25mol/L
NH4H2PO4, flow 1mL/min, Detection wavelength 240nm, the μ L of sample size 15) to be analyzed, external standard is legal
Amount.
Embodiment 1
1.83g manganese acetates and 2.10g cerous nitrates are weighed, 10ml water, the mixing of configuration manganese acetate and cerous nitrate are dissolved in respectively
Solution for later use.12g alumina supports, alumina support compression strength 150N/cm, specific surface area 215m are weighed again2/ g,
Impregnate after the mixed solution containing manganese acetate and cerous nitrate, 100 DEG C of dry 8h, 2h is calcined at 400 DEG C, lead at 300 DEG C
Hydrogen reducing 4h, hydrogen flowing quantity 3L/h.Obtain the MnO of the present embodiment2-CeO2/Al2O3Catalyst.
Produce terephthalaldehyde：It is that solvent prepares 5% dimethyl terephthalate (DMT) solution as raw material using Isosorbide-5-Nitrae dioxane, enters
Stream amount is 1.0ml/min, 350 DEG C of reaction temperature, reaction time 8h.
The MnO that the present embodiment is obtained2-CeO2/Al2O3Catalyst has following performance：The content of manganese oxide is in catalyst
5%, cerium-oxide contents 5%, dimethyl terephthalate (DMT) (DMT) conversion ratio 82.5%, terephthalaldehyde (TPAL) selectivity
For 86.2%.
Embodiment 2
Weigh 4.20g cerous nitrates and be dissolved in 20ml water, then weigh 4.48g manganese nitrate solutions and be made into manganese nitrate and cerous nitrate
Mixed solution, then weighs 12g alumina supports, alumina support compression strength 180N/cm, specific surface area 230m2/ g,
Spray after the mixed solution containing manganese nitrate and cerous nitrate, 120 DEG C of dry 6h, 2h is calcined at 500 DEG C, lead at 320 DEG C
Hydrogen reducing 4h, hydrogen flowing quantity 3L/h.Obtain the MnO of the present embodiment2-CeO2/Al2O3Catalyst.
Produce terephthalaldehyde：It is that solvent prepares 5% dimethyl terephthalate (DMT) solution as raw material using Isosorbide-5-Nitrae dioxane, enters
Stream amount is 0.6ml/min, 370 DEG C of reaction temperature, reaction time 8h.
The palladium-carbon catalyst that the present embodiment is obtained has following performance：The content of manganese oxide is 10% in catalyst, cerium oxide
Content is 10%, dimethyl terephthalate (DMT) (DMT) conversion ratio 84.5%, and terephthalaldehyde (TPAL) is selectively 86.6%.
Embodiment 3
5.6g cerium chlorides are weighed, and are dissolved in 20ml water, 7.92g manganese nitrate solutions is then weighed, is made into cerous nitrate and nitric acid
The mixed solution of manganese.12g alumina supports are weighed again, alumina support compression strength 160N/cm, specific surface area 220
m2/ g, dipping contains after cerous nitrate and manganese nitrate mixed solution, 90 DEG C of dry 9h, 8h is calcined at 300 DEG C, at 320 DEG C
Logical hydrogen reducing 4h, hydrogen flowing quantity 3L/h down.Obtain the MnO of the present embodiment2-CeO2/Al2O3Catalyst.
Produce terephthalaldehyde：It is that solvent prepares 5% dimethyl terephthalate (DMT) solution as raw material using Isosorbide-5-Nitrae dioxane, enters
Stream amount is 1.2ml/min, 380 DEG C of reaction temperature, reaction time 8h.
The palladium-carbon catalyst that the present embodiment is obtained has following performance：The content of manganese oxide is 15% in catalyst, and cerium oxide contains
Measure as 15%, dimethyl terephthalate (DMT) (DMT) conversion ratio 86.5%, terephthalaldehyde (TPAL) is selectively 87.8%.
Embodiment 4
7.32g manganese acetates and 8.38g cerous nitrates are weighed, 15ml water, the mixing of configuration manganese acetate and cerous nitrate are dissolved in respectively
Solution for later use.12g alumina supports, alumina support compression strength 206N/cm, specific surface area 228m are weighed again2/ g,
Impregnate after the mixed solution containing manganese acetate and cerous nitrate, 110 DEG C of dry 4h, 2h is calcined at 600 DEG C, lead at 320 DEG C
Hydrogen reducing 4h, hydrogen flowing quantity 3L/h.Obtain the MnO of the present embodiment2-CeO2/Al2O3Catalyst.
Produce terephthalaldehyde：It is that solvent prepares 5% dimethyl terephthalate (DMT) solution as raw material using Isosorbide-5-Nitrae dioxane, enters
Stream amount is 0.8ml/min, 360 DEG C of reaction temperature, reaction time 8h.
The MnO that the present embodiment is obtained2-CeO2/Al2O3Catalyst has following performance：The content of manganese oxide is in catalyst
20%, cerium-oxide contents 20%.Dimethyl terephthalate (DMT) (DMT) conversion ratio 90.8%, terephthalaldehyde (TPAL) selection
Property is 86.5%.
Comparative example
With urging in the embodiment 1 of Chinese patent CN103508862A (a kind of method that catalysis oxidation prepares terephthalaldehyde)
As a comparison case, the method that the preparation method of terephthalaldehyde is described also referring to the embodiment 1 in the patent document is real for agent
Apply.
10.6g paraxylene is dissolved in 200ml solvent acetonitriles and adds reactor, and adds 3.15g fluorine reagents thereto
The double benzsulfamides of N- fluoro and 5.8g sodium chloride, at room temperature reaction obtain the mixed liquor of paracide；Mixed liquor is without processing
Adding 98wt% sulfuric acid thereto, (paraxylene volume ratio is 1：2) and 8.69g manganese dioxide, room temperature is heated to backflow
Temperature, reacts 5~7 hours；Reaction terminates rear mixed liquor cold filtration, and filtrate adjusts PH to 6~7 with NaOH solution,
Washing separation organic layer, organic layer obtains terephthalaldehyde crude product after vacuum distillation, and crude product is 1 with 100ml volume ratios：
1 ethanol is recrystallized with water mixed liquid, and terephthalaldehyde 85.2g is obtained after drying, paraxylene conversion 79.1% is right
Phthalaldehyde (TPAL) is selectively 80.4%.
Performance test
The test result of the catalyst of embodiment and comparative example see the table below：
Claims (10)
1. a kind of Hydrobon catalyst, it is characterised in that be made up of following component：Counted using the gross weight of Hydrobon catalyst as 100%, the content of manganese oxide is 5~20wt%, and the content of cerium oxide is 5~20wt%, and surplus is aluminum oxide.
2. the preparation method of the Hydrobon catalyst described in claim 1, it is characterised in that first prepare solution containing manganese compound and cerium-containing compound solution respectively, mixed solution is obtained after mixing, mixed solution is contacted with alumina support, then through drying, high-temperature roasting, finally lead to hydrogen reducing, produce.
3. the preparation method of Hydrobon catalyst as claimed in claim 2, it is characterised in that the solution containing manganese compound is any of manganese chloride, manganese acetate, manganese nitrate solution or two or more combinations.
4. the preparation method of above-mentioned Hydrobon catalyst as claimed in claim 2, it is characterised in that described cerium-containing compound solution is any of cerium chloride, cerous nitrate, cerous acetate solution or two or more combinations.
5. the preparation method of Hydrobon catalyst as claimed in claim 2, it is characterised in that the method that the mixed solution is contacted with alumina support is spray or impregnates, time of contact is 0.1~10h.
6. the preparation method of Hydrobon catalyst as claimed in claim 2, it is characterised in that the alumina support compression strength 100~200N/cm, 150~300m of specific surface area2/g。
7. the preparation method of Hydrobon catalyst as claimed in claim 2, it is characterised in that the drying temperature is 80~120 DEG C, the time is 2~10h.
8. the preparation method of Hydrobon catalyst as claimed in claim 2, it is characterised in that the temperature of the high-temperature roasting is 300-600 DEG C, and the time is 1-10h.
9. the preparation method of the Hydrobon catalyst as described in any one of claim 2 to 8, it is characterised in that the temperature of the logical hydrogen reducing is 300-350 DEG C, and the time is 2-6h, hydrogen flowing quantity 3L/h.
10. the method for terephthalaldehyde is produced using the Hydrobon catalyst described in claim 1, it is characterized in that, 30ml Hydrobon catalysts are loaded into reactor, first with 1,4 dioxane are that solvent 5% dimethyl terephthalate (DMT) solution of preparation is raw material, and feed rate is 0.6~2ml/min, 350~380 DEG C of reaction temperature, reaction time 8h, produces terephthalaldehyde.
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| CN1579619A (en) * | 2004-05-20 | 2005-02-16 | 复旦大学 | Mesoporous Mn/Al oxide catalyst, and its preparation method and use |
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| CN102631925A (en) * | 2012-03-30 | 2012-08-15 | 中国科学院山西煤炭化学研究所 | Benzene carboxylic ester hydrogenation catalyst, preparation method thereof and application |
| CN103153930A (en) * | 2010-09-23 | 2013-06-12 | 国际人造丝公司 | Production of alcohols |
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2016
- 2016-04-25 CN CN201610262161.7A patent/CN107303486B/en active Active
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| CN1579619A (en) * | 2004-05-20 | 2005-02-16 | 复旦大学 | Mesoporous Mn/Al oxide catalyst, and its preparation method and use |
| CN101028594A (en) * | 2006-03-01 | 2007-09-05 | 中国科学院生态环境研究中心 | Composite oxide catalyst for cryogenic selective catalystic reductic oxide nitrogen |
| CN101185887A (en) * | 2007-12-20 | 2008-05-28 | 上海交通大学 | Catalyst for wet oxidation technique and preparation method thereof |
| CN101269322A (en) * | 2008-04-25 | 2008-09-24 | 浙江大学 | Load type cerium oxide catalyst for preparing benzaldehyde and preparation method thereof |
| CN103153930A (en) * | 2010-09-23 | 2013-06-12 | 国际人造丝公司 | Production of alcohols |
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